Tunable Lead-salt Diode Laser Research Articles

Effect of the admixture of N2 to low pressure, low temperature H2-CH4-CO2 microwave plasmas used for large area deposition of nanocrystalline diamond films

In a distributed antenna array reactor, microwave H2-CH4-CO2 plasmas with admixture of N2 used for the low-temperature deposition of nanocrystalline diamond (NCD) films are studied by in situ infrared laser absorption spectroscopy (LAS) and optical emission spectroscopy techniques. The experiments are carried out in order to analyze the dependence of temperatures and species densities as a function of the admixture of nitrogen. The evolution of the concentrations of the methyl radical (CH3), and of five stable molecules (NH3, HCN, CH4, C2H2, and CO), are monitored in the plasma processes by LAS using tunable lead salt diode lasers and external-cavity quantum cascade lasers (EC-QCL) as radiation sources. OES is performed simultaneously to obtain complementary information about (i) the degree of dissociation of H2 precursor gas, (ii) the gas temperature and therefore (iii) the density of atomic hydrogen, a key species in the chemistry of NCD deposition plasmas. The species temperatures are not significantly affected by the nitrogen addition. The concentrations of the various species are in the range between 1011 to 1015 molecules cm−3. HCN and CO are the major products in the plasma besides atomic hydrogen. The analysis of the nitrogen and carbon mass balances of the measured species shows that in addition to NH3 and HCN other nitrogen containing species are produced in the plasma which were not probed. It is shown that the formation of HCN consumes C atoms that can be provided from hydrocarbon species and from the deposition of carbon-containing films on the reactor walls, which results in a decrease of the measured densities of hydrocarbon species.

Spectroscopic study of low pressure, low temperature H2–CH4–CO2 microwave plasmas used for large area deposition of nanocrystalline diamond films. Part II: on plasma chemical processes

In a distributed antenna array (DAA) reactor, microwave H2 plasmas with admixtures of 2.5% CH4 and 1% CO2 used for the deposition of nanocrystalline diamond films have been studied by infrared laser absorption and optical emission spectroscopy (OES) techniques. The experiments were carried out in order to analyze the dependence of plasma chemical phenomena on power and pressure at relatively low pressures, up to 0.55 mbar, and power values, up to 3 kW. The evolution of the concentration of the methyl radical, CH3, of five stable molecules, CH4, CO2, CO, C2H2 and C2H6, and of vibrationally excited CO in the first and second hot band was monitored in the plasma processes by in situ infrared laser absorption spectroscopy using tunable lead salt diode lasers (TDL) and an external-cavity quantum cascade laser (EC-QCL) as radiation sources. OES was applied simultaneously to obtain complementary information about the degree of dissociation of the H2 precursor and of its gas temperature. The experimental results are presented in two separate parts. In Part I, the first paper in a two-part series, the measurement of the gas (Tgas), rotational (Trot) and vibrational (Tvib) temperatures of the various species in the complex plasma was the main focus of interest. Depending on the different plasma zones the gas temperature was found to range between about 360 and 1000 K inside the DAA reactor (Nave et al 2016 Plasma Sources Sci. Technol. 25 065002). In Part II, the present paper, taking into account the temperatures determined in the first paper, the concentrations of the various species, which were found to be in a range between 1011 and 1015 cm−3, are the focus of interest. The influence of the discharge parameters power and pressure on the molecular concentrations has been studied. To achieve further insight into general plasma chemical aspects the dissociation of the carbon precursor gases including their fragmentation and conversion to the reaction products has been analyzed in detail.

Spectroscopic studies of microwave plasmas containing hexamethyldisiloxane

Low-pressure microwave discharges containing hexamethyldisiloxane (HMDSO) with admixtures of oxygen and nitrogen, used for the deposition of silicon containing films, have been studied spectroscopically. Optical emission spectroscopy (OES) in the visible spectral range has been combined with infrared laser absorption spectroscopy (IRLAS). The experiments were carried out in order to analyze the dependence of plasma chemical phenomena on power and gas mixture at relatively low pressures, up to 50 Pa, and power values, up to 2 kW. The evolution of the concentration of the methyl radical, CH3, and of seven stable molecules, HMDSO, CH4, C2H2, C2H4, C2H6, CO and CO2, was monitored in the plasma processes by in situ IRLAS using tunable lead salt diode lasers (TDL) and external-cavity quantum cascade lasers (EC-QCL) as radiation sources. To achieve reliable values for the gas temperature inside and outside the plasma bulk as well as for the temperature in the plasma hot and colder zones, which are of great importance for calculation of species concentrations, three different methods based on emission and absorption spectroscopy data of N2, CH3 and CO have been used. In this approach line profile analysis has been combined with spectral simulation methods. The concentrations of the various species, which were found to be in the range between 1011 to 1015 cm−3, are in the focus of interest. The influence of the discharge parameters power, pressure and gas mixture on the molecular concentrations has been studied. To achieve further insight into general plasma chemical aspects the dissociation of the HMDSO precursor gas including its fragmentation and conversion to the reaction products was analyzed in detail.

NH3 Trace Detection Using a Tunable Lead-Salt Diode Laser Near 10 μm

We demonstrate a closed path ammonia gas sensor based on a tunable lead-salt diode laser. In order to measure NH3 concentrations, the laser is scanned over two absorption lines 992.68 and 992.45 cm–1 of the ν2 vibrational band. These lines have free interference patterns with other species in the atmosphere. The experiments are performed with an ammonia mixture in the air at room temperature in an optical multi-path White cell. In our preliminary experiments, a detection limit of ~4 ppb is achieved using direct absorption at 100 mbar pressure and 15 m path length. A detection limit of 0.2 ppb can be reached.

Characterizing a Quantum Cascade Tunable Infrared Laser Differential Absorption Spectrometer (QC-TILDAS) for measurements of atmospheric ammonia

Abstract. A compact, fast-response Quantum Cascade Tunable Infrared Laser Differential Absorption Spectrometer (QC-TILDAS) for measurements of ammonia (NH3) has been evaluated under both laboratory and field conditions. Absorption of radiation from a pulsed, thermoelectrically cooled QC laser occurs at reduced pressure in a 0.5 L multiple pass absorption cell with an effective path length of 76 m. Detection is achieved using a thermoelectrically-cooled Mercury Cadmium Telluride (HgCdTe) infrared detector. A novel sampling inlet was used, consisting of a short, heated, quartz tube with a hydrophobic coating to minimize the adsorption of NH3 to surfaces. The inlet contains a critical orifice that reduces the pressure, a virtual impactor for separation of particles, and additional ports for delivering NH3-free background air and calibration gas standards. The level of noise in this instrument has been found to be 0.23 ppb at 1 Hz. The sampling technique has been compared to the results of a conventional lead salt Tunable Diode Laser Absorption Spectrometer (TDLAS) during a laboratory intercomparison. The effect of humidity and heat on the surface interaction of NH3 with sample tubing was investigated at mixing ratios ranging from 30–1000 ppb. Humidity was seen to worsen the NH3 time response and considerable improvement was observed when using a heated sampling line. A field intercomparison of the QC-TILDAS with a modified Thermo 42CTL chemiluminescence-based analyzer was also performed at Environment Canada's Centre for Atmospheric Research Experiments (CARE) in the rural town of Egbert, ON between May–July 2008. Background tests and calibrations using two different permeation tube sources and an NH3 gas cylinder were regularly carried out throughout the study. Results indicate a very good correlation at 1 min time resolution (R2 = 0.93) between the two instruments at the beginning of the study, when regular background subtraction was applied to the QC-TILDAS. An overall good correlation of R2 = 0.85 was obtained over the entire two month data set, where the majority of the spread can be attributed to differences in inlet design and background subtraction methods.

On-line monitoring of cyclotron target-gas output by means of tunable lead salt diode laser absorption spectroscopy

We demonstrate what is, to our knowledge, the first use of mid-infrared laser absorption spectroscopy for trace-gas measurements of cyclotron target outputs used for the generation of radioactive carbon-11 in positron emission tomography (PET). The spectrometer was based upon a liquid-nitrogen-cooled lead salt diode laser generating single-mode radiation in the wavenumber range of 2230–2240 cm−1. The sample flowed to a multiple-pass optical cell with a total path length of 15.23 m and the laser radiation was detected by two liquid-nitrogen-cooled InSb photodetectors. We present the results of CO, N2O and CO2 measurements on PET trace cyclotron output and discuss future work on 11CO and 11CO2 detection.

Evaluation of Laser Absorption Spectroscopic Techniques for Eddy Covariance Flux Measurements of Ammonia

An intercomparison was made between eddy covariance flux measurements of ammonia by a quantum cascade laser absorption spectrometer (QCLAS) and a lead-salt tunable diode laser absorption spectrometer (TDLAS). The measurements took place in September 2004 and again in April 2005 over a managed grassland site in Southern Scotland, U.K. These were also compared with a flux estimate derived from an "Ammonia Measurement by ANnular Denuder with online Analysis" (AMANDA), using the aerodynamic gradient method (AGM). The concentration and flux measurements from the QCLAS correlated well with those of the TDLAS and the AGM systems when emissions were high, following slurry application to the field. Both the QCLAS and TDLAS, however, underestimated the flux when compared with the AMANDA system, by 64%. A flux loss of 41% due to chemical reaction of ammonia in the QCLAS (and 37% in the TDLAS) sample tube walls was identified and characterized using laboratory tests but did not fully accountforthis difference. Recognizing these uncertainties, the agreement between the systems was nevertheless very close (R2 = 0.95 between the QCLAS and the TDLAS; R2 = 0.84 between the QCLAS and the AMANDA) demonstrating the suitability of the laser absorption methods for quantifying the temporal dynamics of ammonia fluxes.

Performance of a Herriott cell, designed for variable temperatures between 296 and 20 K

We designed, fabricated and tested a multipath Herriott cell (or off-axis spherical mirror interferometer) to achieve low temperature absorption measurements. The cell is fabricated entirely from copper, and the 15 cm radius of curvature copper mirrors have gold coated reflective surfaces. The cell was tested at temperatures between 296 and 20 K with a folded absorption path length of 5.37 m utilizing a lead salt tunable diode laser. Short term temperature stability (1 h) of the Herriott cell is better than 0.005 K under normal operating conditions with a temperature uniformity better than 0.01 K (not measurable). The cell was tested by performing collisional cooling experiments on 13C 16O 2 in helium at temperatures between 70 and 20 K and by performing more traditional pressure broadening and shift measurements on molecular infrared absorption lines at temperatures between 300 and about 80 K on 13C 16O 2 and methane.

Quad quantum cascade laser spectrometer with dual gas cells for the simultaneous analysis of mainstream and sidestream cigarette smoke

A compact, fast response, infrared spectrometer using four pulsed quantum cascade (QC) lasers has been applied to the analysis of gases in mainstream (MS) and sidestream (SS) cigarette smoke. QC lasers have many advantages over the traditional lead-salt tunable diode lasers, including near room temperature operation with thermoelectric cooling and single mode operation with improved long-term stability. The new instrument uses two 36 m, 0.3 l multiple pass absorption gas cells to obtain a time response of 0.1 s for the MS smoke system and 0.4 s for the SS smoke system. The concentrations of ammonia, ethylene, nitric oxide, and carbon dioxide for three different reference cigarettes were measured simultaneously in MS and SS smoke. A data rate of 20 Hz provides sufficient resolution to determine the concentration profiles during each 2 s puff in the MS smoke. Concentration profiles before, during and after the puffs also have been observed for these smoke constituents in SS smoke. Also, simultaneous measurements of CO 2 from a non-dispersive infrared (NDIR) analyzer are obtained for both MS and SS smoke. In addition, during this work, nitrous oxide was detected in both the MS and SS smoke for all reference cigarettes studied.

Quantum Cascade Infrared Laser Spectroscopy for Real-Time Cigarette Smoke Analysis

A compact, fast-response, infrared spectrometer using pulsed quantum cascade (QC) lasers has been applied to the analysis of gases in mainstream and sidestream cigarette smoke. QC lasers have many advantages over the traditional lead salt tunable diode lasers, including near-room-temperature operation with thermoelectric cooling and single mode operation with improved long-term stability. The instrument uses a 36-m, 0.3-L multiple pass absorption gas cell to obtain a time response of 0.1 s for the mainstream system and 0.4 s for the sidestream system. A precision of 10-4 absorbance units in 1 s is achieved using pulse normalization to reduce pulse-to-pulse intensity variations. Laser line widths (hwhm) of 0.006 cm-1 at 967 and 0.010 cm-1 at 1900 cm-1 are obtained in pulsed operation. With this instrument, we have measured the concentrations of ammonia and ethylene using a QC laser at 967 cm-1 and nitric oxide using a laser at 1900 cm-1 in both mainstream and sidestream smoke from two types of cigarettes. ...

Argus: a new instrument for the measurement of the stratospheric dynamical tracers, N 2O and CH 4

We describe here a new instrument for the simultaneous, in situ measurement of the stratospheric tracer molecules, nitrous oxide (N 2O) and methane (CH 4). Argus is unique in its small size making it well suited for limited payload atmospheric research platforms. Argus employs second harmonic spectroscopy using tunable lead–salt diode lasers emitting in the mid-infrared. We first explain the Argus design philosophy followed by detailed descriptions of the instrument's optical, mechanical, and thermal sub-systems. Argus employs an in-flight calibration system providing real time calibrations and tightly constrained uncertainty estimates of the returned data. Data analysis is carried out using non-linear least-squares model fits to the acquired second harmonic spectra. A sampling of Argus data acquired on a recent stratospheric research campaign in the Arctic winter is presented.

Stimulated laser Raman processes in low-density Rydberg matter: Wave number and intensity blueshifts

Wave-number blueshifts of single-mode laser light in low-density Rydberg matter are found to be due to stimulated Raman processes. The Rydberg matter is mainly formed from Rydberg states of K atoms. The lasers used are mW continuous-wave lasers in the ir, lead-salt tunable diode lasers. Of special significance is the blueshifting observed as shifts of Fabry-Perot etalon fringes of the order of 0.05 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$. This blueshifting is explained as due to complete conversion to anti-Stokes radiation through higher-order stimulated Raman shifting by extremely small quanta from the near continuum of energy levels in the metallic Rydberg matter phase. Complicated strong shifts of intensity to larger wave numbers in the laser modes are also observed, due to coupling of laser side modes to the anti-Stokes waves. The high efficiency of the stimulated Raman process is partly due to the weak coupling to other degrees of freedom.

Airborne Laser Infrared Absorption Spectrometer (ALIAS-II) for in situ atmospheric measurements of N_2O, CH_4, CO, HCL, and NO_2 from balloon or remotely piloted aircraft platforms

The Airborne Laser Infrared Absorption Spectrometer II (ALIAS-II) is a lightweight, high-resolution (0.0003-cm(-1)), scanning, mid-infrared absorption spectrometer based on cooled (80 K) lead-salt tunable diode laser sources. It is designed to make in situ measurements in the lower and middle stratosphere on either a balloon platform or high-altitude remotely piloted aircraft. Chemical species that can be measured precisely include long-lived tracers N(2)O and CH(4), the shorter-lived tracer CO, and chemically active species HCl and NO(2). Advances in electronic instrumentation developed for ALIAS-I, with the experience of more than 250 flights on board NASA's ER-2 aircraft, have been implemented in ALIAS-II. The two-channel spectrometer features an open cradle, multipass absorption cell to ensure minimal contamination from inlet and surfaces. Time resolution of the instrument is <or=3 s, allowing rapid in situ measurements with excellent spatial resolution. ALIAS-II has completed successful balloon flights from New Mexico, Alaska, and Brazil providing CH(4) and N(2)O vertical profiles in the tropics, mid-latitudes, and high northern latitudes up to altitudes of 32 km.

High-resolution PIRSS using a tunable infrared diode laser: the Davydov doublet of the antiferroelectric (2 × 1) monolayer CO adsorbed on NaCl(001)

The temperature dependence of the Davydov doublet of the antiferroelectric (2 × 1) monolayer CONaCl(001) has been studied between 11 and 25 K by means of polarization infrared surface spectroscopy (PIRSS) using a tunable lead salt diode laser with a resolution better than 5 × 10 −3cm −1. At 11 K the linewidth of the symmetric vibrational exciton, polarized perpendicular to the surface, was determined to be 0.035 cm −1, the linewidth of the antisymmetric vibrational exciton, polarized parallel to the surface, to be 0.025 cm −1, the sharpest spectral line of an adsorbate observed. To obtain phase relaxation times T 2 in the low-temperature region, we fitted the parameters of the exchange dephasing model to the experimental data. A satisfactory fit for both the frequency and the linewidth is obtained at temperatures below 25 K. Above 25 K the antisymmetric vibrational exciton becomes extremely broad and finally disappears, and a successful fit was obtained only for the linewidth of the symmetric vibrational exciton. It is shown how the vibrational energy relaxation time T 1 may be obtained by varying the spectral power of the laser light.

Stabilizing Lead-Salt Diode Lasers: Understanding and Controlling Chaotic Frequency Emission

Lead-salt tunable diode lasers (TDLs) are the only devices currently available that can generate tunable monochromatic radiation at arbitrary wavelengths between 3 and 30 micrometers and are particularly useful for high-resolution spectroscopy over a wide range of spectral regimes. Detailed observations of TDLs show that the observed instrumental linewidth is actually a temporal average of many narrow (less than 0.5 megahertz) emission "modes." The time scale characteristic of these "modes," which appear to be of relatively constant intensity, is of the order of a microsecond. The laser's behavior is highly suggestive of a chaotic process, that is, seemingly random excursions of a dynamic variable (frequency) within a bounded range. This report shows experimentally that TDL emissions are indeed chaotic. Furthermore, in a simple and robust fashion, this chaotic behavior has been successfully controlled with the use of recent techniques that take advantage of chaos to produce a narrow band laser output.

Experiments on linewidth reduction by fast electrical feedback

We report our first results on broadband electrical feedback applied to tunable lead-salt diode lasers. We use a heterodyne technique in combination with electronic frequency discrimination to reduce the diode-laser linewidth. The loop band width is about 10 MHz. We present results on high-frequency modulation to study the frequency response of the diode laser. From this experiment we are able to estimate the carrier tuning rate of the used lead-salt diode laser. Preliminary results in linewidth reduction by fast electrical feedback promise the possibility to apply the fast electrical feedback technique to lead-salt diode lasers.

Optoacoustic Lead-Salt Diode Laser Detection of Trace Species in a Flow System

An experimental setup for kinetic and product studies in a flow system has been developed. For detection, a nonresonant optoacoustic technique combined with a tunable lead-salt diode laser has been employed. The performance of the system was tested on ammonia in argon, and a detection limit (S/N = 2) of 8 × 1012 molecules cm−3 (corresponding to 320 ppb at atmospheric pressure) was obtained at a pressure of about 7 kPa when frequency modulation was employed. At 1.5 kPa the detection limit was about 2 × 1014 molecules cm−1. With a multipass cell the sensitivity was increased by a factor of four.

Optical heterodyne detection and microwave rectification up to 26 GHz using quantum well infrared photodetectors

We have demonstrated heterodyne detection up to an intermediate frequency of 26.5 GHz using quantum well infrared photodetectors. A CO/sub 2/ laser and a lead-salt tunable diode laser were used as the infrared sources. Heterodyne detection experiments measure the high frequency behavior of photoexcited electrons and their transport properties. We have also carried out microwave rectification experiments which measure the high frequency behavior associated with the dark-current electron-transport processes.

Absorption spectroscopy of N_2O with phase-diffusion-noise sidebands on a lead-salt tunable diode laser

The broad phase-diffusion-noise spectrum of a lead-salt tunable diode laser (TDL) has been exploited for the detection of absorbances produced from low-pressure N(2)O vapor in the 4.47-µm spectral region. This effect has previously been observed in the detection of electronic transitions in rubidium, cesium, and molecular oxygen with anAlGaAs TDL operating in the 0.700-0.800-µm region. For the first time to our knowledge, this paper presents evidence of this phenomenon when a midinfrared rovibrational absorption line is monitored. The technique is also compared with traditional TDL spectroscopic methods for its applicability to trace-vapor monitoring.

Stabilization of 3.3 and 5.1 μm lead-salt diode lasers by optical feedback

Optical stabilization of tunable lead-salt diode lasers (TDL) in the mid-infrared is presented for the first time. By introducing an external feedback mirror both the linewidth is substantially narrowed and the frequency of the TDL is stabilized and controlled via this mirror in a frequency-offset locked scheme. We achieved narrowing of the linewidth by 1–2 orders of magnitude or better. The TDL is offset-locked to a CO gas laser by a heterodyne technique: the beatnote between the two lasers is used to control the length of the external resonator. By this scheme we gain the capability of absolute frequency measurements with sub-Doppler accuracy. The improved spectral properties of the diode laser provide a new tool for high-resolution molecular spectroscopy in the mid-infrared.